Systematic Green Solvent Selection for the Hydroformylation of Long-Chain Alkenes

Abstract

When selecting solvents, not only thermodynamic criteria but also environmental, health, and safety (EHS) properties should be considered. To this end, we present a fully automated solvent selection approach for the homogeneous catalyzed hydroformylation of 1-decene in a temperature-dependent thermomorphic multicomponent system (TMS) using the conductor-like screening model for real solvents (COSMO-RS). The state-of-the-art TMS uses N,N-dimethylformamide (DMF) as the catalyst carrier, which is developmentally toxic, thereby demanding replacement. In order to evaluate the EHS properties holistically, 30 predictive EHS models for 15 different properties are considered in the solvent selection framework, as well as the reliability of the predictions. From a database containing approximately 7800 molecules, the most promising candidates are identified. The best solvent among them, diethyl sulfoxide (DESO), is predicted as outperforming DMF as a catalyst solvent in the hydroformylation. The evidence suggests that DESO may be a broadly applicable environmentally benign substitute solvent for DMF.

The green solvent: a critical perspective

“…A wealth of additional studies, too many to survey comprehensively, have focussed more narrowly on the replacement of: (i) a single solvent, such as N -methylpyrrolidone (Sherwood et al 2016 ) or N,N- dimethylformamide (Linke et al 2020 ); (ii) a solvent type, such as dipolar aprotics (Duereh et al 2017 ) or chlorinated organics (Jordan et al 2021 ); (iii) a reaction medium for a particular reaction (Avalos et al 2006 ), such as amide coupling (MacMillan et al 2013 ), aldehyde reductive amination (McGonagle et al 2013 ) or the Delépine reaction (Jordan et al 2020 ); (iv) a solvent in a process (Avalos et al 2006 ; Fadel and Tarabieh 2019 ), such as membrane production (Xie et al 2020 ); (v) one or more solvents in a series of products (Isoni et al 2016 ); (vi) one or more solvents in an application, such as cleaning, (Tickner et al 2021 ), lubrication (Dörr et al 2019 ), chromatography (Taygerly et al 2012 ; MacMillan et al 2012 ), or product recovery (López-Porfiri et al 2020 ); (vii) one or more solvents in a technology, such as carbon capture (Borhani and Wang 2019 ), or water-based metal extraction (Binnemans and Jones 2017 ; Peeters et al 2020 ); or (viii) the optimised selection of solvents and anti-solvents in pharmaceutical recrystallization from a defined set of 68 compounds (Tan et al 2019 ).…”

“…Most of these have been assembled from various compilations and data sets used in the computerised identification and selection of solvents with particular characteristics and are discussed in “ Solvent selection and design: empirical database and computational methods ” section. Some materials cited as green in additional papers [and from one website ( http://www.xftechnologies.com/solvents )] are also included (Bankar et al 2013 ; Barbaro et al 2020 ; Bauer and Kruse 2019 ; Bergez-Lacoste et al 2014 ; Byrne et al 2017 ; Byrne et al 2018 ; Calvo‑Flores et al 2018 ; Christy et al 2018 ; Clark et al 2017a ; Cseri and Szekely 2019 ; Di Girolamo et al 2021 ; Diorazio et al 2016 ; Driver and Hunter 2020 ; Estévez 2009 ; Gevorgyan et al 2020 ; Ho et al 2020 ; Hu et al 2014 ; Jessop et al 2012 ; Jin et al 2017 ; Kobayashi et al 2019 ; Lee et al 2017 ; Linke et al 2020 ; Marcel et al 2019 ; Moity et al 2014a , b ; Mudraboyina et al 2016 ; Murray et al 2016 ; Pellis et al 2019 ; Piccione et al 2019 ; Qian et al 2021 ; Samorì et al 2014 ; Shahbazi et al 2020 ; Shakeel et al 2014 ; Sherwood et al 2016 ; Strohmann et al 2019 ; Tobiszewski et al 2015 ; Vinci et al 2007 ; Wypych and Wypych 2014 , 2019 ; Yang and Sen 2010 ; Yara-Varón et al 2016; Zhenova et al 2019 ).…”

Forschungsarbeiten am Institut für Verfahrenstechnik der Otto‐von‐Guericke‐Universität Magdeburg

“…Um Kriterien der Umweltverträglichheit (EHS: Environmental, Health, Safety) bei der Auswahl von Lösungsmitteln angemessen zu berücksichtigen, wurden automatisierte Screening‐Methoden für große Stoffdatenbanken entwickelt. Damit konnte für das Beispiel der Hydroformylierung langkettiger Olefine die Substanz Diethylsulfoxid (DESO) als Ersatzstoff für das bisher verwendete entwicklungstoxische Lösungsmittel N,N‐Dimethylformamid (DMF) identifiziert werden 14. DESO erwies sich nicht nur als umweltfreundliches Lösungsmittel für den eingesetzten homogenen Rhodium‐Katalysator, sondern auch als sehr geeigneter Hilfsstoff für die Katalysatorrückgewinnung aus dem Reaktionsgemisch.…”

Computer-aided solvent screening for the fractionation of wet microalgae biomass

“…Recently, Linke et al developed a COSMO-RS-based solvent screening for catalyst recovery in thermomorphic solvent systems by using QSAR models from VEGA for the prediction of EHS properties and the selection of green solvents which served as a starting point of this study. 62 Our goal is to identify solvents for the extraction and fractionation of wet algae biomass by a computer-guided approach. A database containing more than 8000 molecules was screened in silico in order to identify suitable solvents for each biomass fraction of the model microalga P. tricornutum.…”

“…Similar to Linke et al, QSAR models from VEGA were applied to predict selected EHS properties of the solvent candidates. 62 The most promising solvent candidates obtained from the computational predictions were then evaluated experimentally. Finally, a biorefinery process concept for the wet fractionation of P. tricornutum was proposed.…”